CN114340874B - Device, system, method for post-curing product and post-cured product - Google Patents

Abstract

A device (1000) includes a housing (110), a chamber (120) disposed in the housing, at least two Light Emitting Diodes (LEDs) (130) disposed within the housing (110), and a user interface (140) disposed on an exterior (112) of the housing. The chamber (120) may be adapted for each of an open configuration, a closed configuration, and a hermetically sealed configuration. The chamber (120) contains a material transparent to actinic radiation and light from the LEDs (130) enters the chamber from more than one direction. The user interface (140) includes a display (142) and a program switch (144) configured to adjust at least three operating parameters of the device. The apparatus (1000) further includes a vacuum pump (150) operably coupled to the chamber (120). A system includes an apparatus (1000) and an article (180). An article includes at least one layer of a photopolymerizable crosslinking composition and a low extractable component content. A method of post-curing an article comprising: obtaining an article (180); placing the article in an apparatus (1000); inputting a post-cure program or accessing a saved post-cure program through the user interface (140); and running the post-curing program. The post-cure procedure includes: light intensity provided by a light source (130); and the length of time of the light provided by the light source (130); and a delay time between initiation of light provided by the light source (130) and initiation of evacuation by the vacuum pump (150) and/or a delay time between initiation of evacuation by the vacuum pump (150) on the interior of the chamber (120) and initiation of light provided by the light source (130).

Description

Apparatus, system, method for post-curing articles, and post-cured articles

Technical Field

The present disclosure broadly relates to apparatus, methods, and post-cured articles for post-curing articles.

Background

Devices for radiation curing articles have been used in many industries; however, improvements in performance and user control of the device are still needed.

Disclosure of Invention

In a first aspect, an apparatus is provided. The apparatus includes: a) A housing; b) A chamber disposed in the housing; c) At least two Light Emitting Diodes (LEDs) disposed within the housing; and a user interface disposed on an exterior of the housing. The chamber is configured to be adaptable to each of an open configuration, a closed configuration, and a hermetically sealed configuration, and the chamber comprises a material transparent to actinic radiation. Light from at least two LEDs enters the chamber from more than one direction. The user interface includes a display and a plurality of program switches configured to adjust at least three operating parameters of the device. The apparatus also includes a vacuum pump operatively connected to the chamber.

In a second aspect, an article is provided. The article includes multiple layers of at least one photopolymerizable crosslinking composition. In addition, when extraction is performed with a 5% by volume aqueous ethanol solution, the article comprises 0.1% by weight or less of extractable components, based on the total weight of the article. The product is prepared by the following process: a) Obtaining a photopolymerizable composition; b) Selectively curing the photopolymerizable composition using actinic radiation to form an article having a plurality of layers of at least one photopolymerizable composition; c) Removing excess photopolymerizable composition from the article; d) Placing the article in the apparatus of the first aspect; e) Inputting a post-curing program or accessing the saved post-curing program through a user interface; and f) running a post-cure program. The post-cure procedure included: i) The light intensity provided by at least two LEDs; ii) the length of time of the light provided by the at least two LEDs; and at least one of the following: iiia) a delay time between initiation of light provided by the at least two LEDs and initiation of evacuation by the vacuum pump, or iiib) a delay time between initiation of evacuation by the vacuum pump on the interior of the chamber and initiation of light provided by the at least two LEDs.

In a third aspect, a method of post-curing an article is provided. The method comprises the following steps: a) Obtaining an article; b) Placing the article in an apparatus; c) Inputting a post-curing program or accessing the saved post-curing program through a user interface; and d) running a post-cure program. The apparatus includes: 1) A housing; 2) A chamber disposed in the housing; 3) At least one light source disposed within the housing; 4) A user interface disposed on an exterior of the housing, the user interface including a display and a plurality of program switches configured to adjust at least three operating parameters of the device; and 5) a vacuum pump operatively connected to the chamber. The post-cure procedure included: i) Light intensity provided by at least one light source; ii) a length of time of light provided by the at least one light source; and at least one of the following: iiia) a delay time between initiation of light provided by the at least one light source and initiation of evacuation by the vacuum pump, or iiib) a delay time between initiation of evacuation by the vacuum pump on the interior of the chamber and initiation of light provided by the at least one light source.

In a fourth aspect, another article is provided. The article is prepared by the method of the third aspect.

In a fifth aspect, a system is provided. The system comprises: a) The apparatus of the first aspect; and b) an article comprising at least one photopolymerizable composition.

It has been found that the device of the present disclosure can provide greater user control than previous devices. Further, methods of using apparatus and post-cured articles according to at least certain embodiments of the present disclosure are found to provide articles having low extractables content, for example, as compared to the alternative use of other post-curing methods.

The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The following description more particularly exemplifies illustrative embodiments. Guidance is provided through a list of embodiments that can be used in various combinations throughout this disclosure. In each case, the recited list serves only as a representative group and should not be construed as an exclusive list.

Drawings

Fig. 1A is a general schematic diagram of an exemplary device.

FIG. 1B is a general schematic of an exemplary system including an apparatus and article of manufacture.

FIG. 1C is a general schematic of a system including an exemplary device and a portion of an exemplary article of manufacture.

FIG. 1D is a general schematic of another system including an exemplary device and a portion of an exemplary article of manufacture.

FIG. 1E is a general schematic diagram of an exemplary user interface.

Fig. 2 is a general schematic diagram of a stereolithography apparatus.

Fig. 3 is an isometric view of an exemplary article.

FIG. 4 is a flow chart of an exemplary process for preparing an article.

FIG. 5 is a flow chart of an exemplary process for post-curing an article.

Fig. 6 is a block diagram of a general system 600 for laminate manufacturing of an article.

Fig. 7 is a block diagram of a general manufacturing process for an article.

FIG. 8 is a high-level flow chart of an exemplary article manufacturing process.

FIG. 9 is a high-level flow chart of an exemplary article stack manufacturing process.

Fig. 10 is a schematic front view of an exemplary computing device 1000.

While the above-identified drawing figures set forth several embodiments of the disclosure, other embodiments are also contemplated, as noted in the specification. The figures are not necessarily drawn to scale. Not every feature is illustrated in every figure. In all cases, this disclosure presents the invention by way of representation and not limitation.

Detailed Description

As used herein, in the context of a composition being substantially free of components, the term "substantially free" means that the composition comprises less than 1 weight percent (wt.%), 0.5 wt.% or less, 0.25 wt.% or less, 0.1 wt.% or less, 0.05 wt.% or less, 0.001 wt.% or less, or 0.0001 wt.% or less of components, based on the total weight of the composition.

As used herein, the term "polymeric" refers to a polymer comprising at least one polymer.

As used herein, the term "cavity" refers to an empty space defined by at least one wall of a (e.g., solid) object.

As used herein, "curing" means hardening or partially hardening the composition by any mechanism, such as by heat, light, radiation, electron beam, microwaves, chemical reactions, or combinations thereof. As used herein, the term "hardenable" refers to a material that can be cured or set, for example, by heating to remove solvent, heating to cause polymerization, chemical crosslinking, radiation-induced polymerization or crosslinking, and the like. As used herein, "cured" refers to a material or composition that has been hardened or partially hardened (e.g., polymerized or crosslinked) by curing.

As used herein, "transparent" refers to a material having a thickness of 10 millimeters or less and having at least 50% transmission, 70% transmission, or optionally greater than 90% transmission over a particular wavelength range.

The words "preferred" and "preferably" refer to embodiments of the present disclosure that may provide certain benefits in certain circumstances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the present disclosure.

In the present application, terms such as "a", "an", and "the" are not intended to refer to only a single entity, but include general categories, specific examples of which may be used for illustration. The terms "a," an, "and" the "are used interchangeably with the term" at least one. The phrases "at least one of … … (seed)" and "at least one of … … (seed)" of a successor list refer to any one of the items in the list and any combination of two or more of the items in the list.

As used herein, the term "or" is generally employed in its sense including "and/or" unless the context clearly dictates otherwise. The term "and/or" means one or all of the listed elements, or a combination of any two or more of the listed elements.

Also, all numerical values herein are assumed to be modified by the term "about" and preferably by the term "precisely". As used herein, with respect to a measured quantity, the term "about" refers to a deviation in the measured quantity that is commensurate with the objective of the measurement and the accuracy of the measurement device used, as would be expected by a skilled artisan taking the measurement with some care.

As used herein, as a modifier to a characteristic or property, the term "substantially" means that the characteristic or property will be readily identifiable by a person of ordinary skill without requiring an absolute precision or perfect match (e.g., within +/-20% for a quantifiable characteristic), unless specifically defined otherwise. Unless specifically defined otherwise, the term "substantially" means a high degree of approximation (e.g., within +/-10% for quantifiable characteristics), but again does not require an absolute precision or perfect match. Terms such as identical, equal, uniform, constant, strict, etc. should be understood to be within ordinary tolerances, or within measurement errors applicable to a particular situation, rather than requiring absolute accuracy or perfect matching.

Apparatus and method for controlling the operation of a device

In a first aspect, the present disclosure provides an apparatus. The apparatus includes:

a) A housing;

b) A chamber disposed in the housing, the chamber configured to be adaptable to each of an open configuration, a closed configuration, and a hermetically sealed configuration, wherein the chamber comprises a material transparent to actinic radiation;

c) At least two Light Emitting Diodes (LEDs) disposed within the housing, wherein light from the at least two LEDs enters the chamber from more than one direction;

d) A user interface disposed on an exterior of the housing, the user interface including a display and a plurality of program switches configured to adjust at least three operating parameters of the device; and

E) A vacuum pump operatively connected to the chamber.

Devices in accordance with at least some embodiments of the present disclosure advantageously provide increased user control of the operation of the device.

Referring to fig. 1A to 1D, an apparatus 1000 according to the first aspect includes a housing 110 and a chamber 120 provided in the housing 110. The housing 110 is typically formed of a polymeric material, metal, and/or glass. The chamber 120 is configured to be adaptable to each of an open configuration (fig. 1A, wherein the hinge cover 122 is raised to allow access to the interior of the chamber 120), a closed configuration (fig. 1B, wherein the hinge cover 122 is closed), and a hermetically sealed configuration (fig. 1C, wherein the hinge cover 122 is closed and the atmosphere cannot leave or enter the chamber due to the presence of the flexible sealing element 123 that can be seen in fig. 1A). The inclusion of flexible sealing element 123 facilitates the ability to regulate the pressure inside chamber 120 and maintain a selected pressure within chamber 120 (e.g., using vacuum pump 150) when hinge cover 122 is closed. One suitable flexible sealing element is a rubber O-ring.

The chamber 120 contains a material that is transparent to actinic radiation. For example, the chamber may contain a material that is transparent to actinic radiation having the following wavelengths: at least 250 nanometers (nm), 300nm or more, 350nm or more, 400nm or more, 450nm or more, 500nm or more, 550nm or more, or 600nm or more; and 900nm or less, 850nm or less, 800nm or less, 750nm or less, 700nm or less, or 650nm or less. In other words, the material of at least a portion of the preparation chamber is transparent to actinic radiation between 250nm and 900nm or between 250nm and 650 nm. Suitable materials for at least a portion of the preparation chamber that are transparent to actinic radiation include glass and quartz. For example, but not limited to, in some embodiments, the chamber 120 includes at least two, at least three, or at least four glass walls through which the actinic radiation enters the chamber. In some embodiments, the chamber 120 includes at least two, at least three, or at least four quartz walls through which the actinic radiation enters the chamber. If desired, a combination of glass and quartz may be contained in the same chamber. In the embodiment shown in fig. 1A-1D, the chamber 120 is cylindrical and has one curved sidewall.

At least two Light Emitting Diodes (LEDs) 130 are disposed within the housing 110 such that light from the at least two LEDs 130 enters the chamber 120 from more than one direction. In some embodiments, the first LED is positioned to direct light through a first major surface 121 of the chamber and the second LED is positioned to direct light through an opposite second major surface 123 of the chamber. In other embodiments, the floor of the chamber is the first major surface of the chamber and the lid 122 of the chamber is the second major surface of the chamber. Referring to fig. 1B, in some embodiments, the apparatus 1000 further comprises a third LED positioned to direct light through the third major surface 125 of the chamber, wherein the third major surface 125 is directly adjacent to each of the first major surface 121 of the chamber and the second major surface 123 of the chamber. Similarly, in some embodiments, the device 1000 further comprises a fourth LED positioned to direct light through a fourth major surface 127 of the chamber, wherein the fourth major surface 127 is opposite the third major surface 125 of the chamber. The use of at least two LEDs to direct light from different directions may facilitate exposing at most the entire sample to radiation simultaneously during the post-curing process. It should be understood that reference to "a first LED" encompasses the presence of more than one LED located at the location of the first LED, e.g., an array of individual LED bulbs may be provided as each of the first LED, the second LED, etc., rather than limiting the "first LED" to a single LED bulb.

In some embodiments, each of the LEDs provides light having a peak wavelength between 250nm and 500 nm. In certain embodiments, there are at least two LEDs that provide light having a peak wavelength below 360nm, above 460nm, or both. Preferably, the (e.g., at least two) LEDs provide the following light intensities: 50 milliwatts per square centimeter (mW/cm ²) or greater, 100mW/cm ² or greater, 150mW/cm ² or greater, 200mW/cm ² or greater, 250mW/cm ² or greater, or 300mW/cm ² or greater; and 500mW/cm ² or less, 450mW/cm ² or less, 400mW/cm ² or less, or 350mW/cm ² or less. In other words, the LEDs may provide a light intensity of 50mW/cm ² to 500mW/cm ² or 300mW/cm ² to 500mW/cm ².

Referring to fig. 1D, in some embodiments, the apparatus 1000 further includes a diffusing element 135 disposed between the at least one LED 130 and the chamber 120. The diffusing element is an optical element or collection of elements having a light transmittance of at least 50%. The diffusing element may be a volume diffuser, such as a diffuser plate or foam. These diffusing elements may also be surface diffusers, diffractive or holographic diffusers, bead coated substrates or surface structures on substrates. Exemplary surface diffusers are available as, for example, optical frosted glass diffusers from the company baston, eppend Optics inc. The apparatus may include a diffusing element positioned to diffuse light provided from any one or more of the light sources; for example, a device with four light sources may include one, two, three, or four separate diffusing elements.

In many embodiments, the apparatus 1000 also includes a reflective material 132 positioned in the housing 110 to reflect actinic radiation through either the first major surface 121 of the chamber or the opposite second major surface 123 of the chamber. Suitable reflective materials include, for example, but are not limited to, metals such as aluminum or silver. The reflective material is optionally a self-supporting layer or a coating on a substrate (e.g., a polymer substrate and/or a glass substrate).

The device 1000 also includes a user interface 140 disposed on the exterior 112 of the housing. The user interface 140 includes a display 142 and a plurality of program switches 144 configured to adjust at least three operating parameters of the device. In addition, the apparatus 1000 includes a vacuum pump 150 that is operatively connected (e.g., cured) to the chamber 120, such as using tubing 152 connected to the vacuum pump 150 and the chamber 120, such that the vacuum pump and the chamber are in fluid communication with each other. As used herein, "operably connected" refers to two structures and/or devices that are attached (directly or indirectly) to enable each structure and/or device to function with another structure and/or device. For example, a vacuum pump may be operatively connected to the chamber using tubing, wherein the vacuum pump reduces the pressure in the chamber by drawing a vacuum through the tubing between the vacuum pump and the chamber to draw gas from the chamber. The advantage of using vacuum evacuation of the chamber is that if the vacuum evacuation is present in a particular article disposed in the chamber, it will assist in removing volatile components from the article. Further, oxygen may be a cure inhibitor, so removing ambient oxygen from the chamber may help to increase the degree of cure, the rate of cure, or both, during post-cure of the article.

Preferably, the vacuum pump is configured to achieve the following absolute pressures inside the chamber: 0.1 millibar (mbar) or more, 0.25mbar or more, 0.5mbar or more, 0.75mbar or more, 1mbar or more, 2mbar or more, 3mbar or more, 4mbar or more, or 5mbar or more; and 30mbar or less, 27mbar or less, 25mbar or less, 23mbar or less, 20mbar or less, 17mbar or less, 15mbar or less, 12mbar or less, or 10mbar or less. In other words, the vacuum pump may be configured to achieve an absolute pressure of 0.1 to 30mbar, 5 to 20mbar or 0.1 to 10mbar inside the chamber. The degree of vacuum within the chamber may vary depending on the particular application. In the embodiment shown in fig. 1B, vacuum pump 150 is located on the exterior of housing 110, and an optional three-way valve 154 is shown connecting chamber 120 to vacuum pump 150 and/or to gas source 160. The three-way valve 154 is also connected to tubing 162 that is connected to a gas source 160. Other typical connectors, such as fittings or valves, may optionally be used in conjunction with the vacuum pump 150. In the embodiment shown in fig. 1D, the vacuum pump 150 is located within the housing 110, and the first valve 156 and the second valve 166 are each operatively connected to the chamber 120 (e.g., via tubing 152 and 162, respectively). The first valve 156 may operatively connect the chamber 120 to the vacuum pump 150 and the second valve 166 operatively connects the chamber 120 to the gas source 160. Suitable gas sources include, for example, a container (e.g., a pressurized gas cylinder) containing a compressed gas (e.g., an inert gas). Typical inert gases for use with the apparatus include nitrogen, argon and/or helium. The advantage of using both vacuum and gas is to provide control over the content of the atmosphere throughout the chamber. This is in contrast to the following: the gas is introduced into the chamber without first removing the ambient atmosphere, wherein there is a possibility that the gas does not completely displace the ambient atmosphere, especially around the article to be post-cured.

Referring to fig. 1B, an exemplary apparatus 1000 is shown in which an optional relief valve 155 operably connects chamber 120 to the exterior of housing 110, such as through tubing 157. In use, the relief valve provides a conduit through which pressure can be equalised between the interior of the chamber and the ambient pressure outside the device. This is advantageous in that the lid of the chamber can be opened after the vacuum or gas in the chamber has been used.

To accommodate pressure variations, the chamber 120 is preferably formed of a material capable of maintaining its structural integrity under a range of internal pressures. In one embodiment, the chamber comprises toughened safety glass having a compressive strength of 700N/mm to 900N/mm. The glass thickness can be calculated according to DIN standard 7080:2005-05 "pressure resistant round glass for borosilicate glass is not limited in the low temperature range". The glass thickness required for a particular chamber depends on the size of the chamber being formed. One suitable glass thickness is about 5 millimeters.

Referring to FIG. 1E, an exemplary user interface 140 is shown. The user interface 140 has a display 142 and a plurality of program switches 144 including at least one button, at least one knob (e.g., in fig. 1B), or a combination thereof. The embodiment shown in fig. 1E includes eleven buttons 144. Any number of buttons 144 (or knobs) may be dedicated to increasing or decreasing selected values of parameters such as gas purge time, light intensity (e.g., power), vacuum delay time, and/or light emission time. Typically, the user interface includes an activation button 146 that may be configured (e.g., electrically coupled to the LED) such that pressing the activation button initiates the light emitted by the LED. Optionally, a start button 146 is configured (e.g., electrically coupled to the program switch 144) to initiate a program that has been entered via the user interface. In some embodiments, the user interface 140 includes a touch screen 143 that provides a display and a plurality of program switches (e.g., in fig. 1C). In other embodiments, the display 142 is not a touch screen. Advantageously, in some embodiments, the program switch 144 is further configured to adjust the time to purge the chamber 120 with gas from the gas source 160, the pressure to purge the chamber 120 with gas, or both.

Referring again to fig. 1B, in some embodiments, the apparatus 1000 further comprises a processor 170. The processor 170 causes (e.g., at least two) LEDs 130 to emit light and causes the vacuum pump 150 to operate according to a program input through the user interface 140. Any suitable computer processor may be incorporated into the device. In selected embodiments, the processor 170 further includes a memory 172 that provides the ability to cause the LED 130 to emit light and/or to cause the vacuum pump 150 to operate according to a program stored in the memory 172. The processor 170 is electrically coupled to the user interface 140 either wirelessly or physically via an electrical connection. The advantage of including a memory is that the device will have the following capabilities: the program that has been run is recorded and optionally details of the post-cure program for the particular article (especially for articles requiring regulatory approval) are reported.

In some embodiments, the operating parameters of the device that are adjustable by the user interface include: 1) The intensity of light provided by the LED; 2) The length of time of the light provided by the LED; and 3) a delay time between initiation of the light provided by the LED and initiation of the evacuation of the vacuum on the interior of the chamber by the vacuum pump. In some embodiments, the operating parameters of the device that are adjustable by the user interface include: 1) The intensity of light provided by the LED; 2) The length of time of the light provided by the LED; and 3) a delay time between initiation of the vacuum pump drawing a vacuum on the interior of the chamber and initiation of the light provided by the LED. Thus, the user has the option of ordering and timing the execution of the post-cure steps, and the post-cure process for a particular sample can be tailored by selecting a variation of these operating parameters.

Suitable lengths of time for the light to be provided by the LED include: 1 minute or more, 2 minutes or more, 3 minutes or more, 4 minutes or more, 5 minutes or more, 6 minutes or more, 7 minutes or more, 8 minutes or more, 9 minutes or more, 10 minutes or more, 11 minutes or more, 13 minutes or more, 15 minutes or more, 16 minutes or more, 18 minutes or more, or 20 minutes or more; and 180 minutes or less, 150 minutes or less, 125 minutes or less, 100 minutes or less, 80 minutes or less, 60 minutes or less, 40 minutes or less, 30 minutes or less, 25 minutes or less, or 21 minutes or less, 18 minutes or less, 16 minutes or less, or 12 minutes or less, such as 7 minutes to 25 minutes.

Suitable times between initiation of the light provided by the LED and initiation of the vacuum pump drawing a vacuum on the interior of the chamber include: 5 seconds or more, 7 seconds or more, 10 seconds or more, 12 seconds or more, 15 seconds or more, 25 seconds or more, 30 seconds or more, 40 seconds or more, 50 seconds or more, 60 seconds or more, or 70 seconds or more; and 15 minutes or less, 13 minutes or less, 11 minutes or less, 9 minutes or less, 7 minutes or less, 5 minutes or less, 3 minutes or less, 2 minutes or less, or 1 minute or less, such as 10 seconds to 3 minutes.

Suitable times between initiation of the vacuum pump drawing a vacuum on the interior of the chamber and initiation of the light provided by the LED include: 5 seconds or more, 7 seconds or more, 10 seconds or more, 12 seconds or more, 15 seconds or more, 25 seconds or more, 30 seconds or more, 40 seconds or more, 50 seconds or more, 60 seconds or more, or 70 seconds or more; and 5 minutes or less, 4.5 minutes or less, 4 minutes or less, 3.5 minutes or less, 3 minutes or less, 2.5 minutes or less, 2 minutes or less, 1.5 minutes or less, 1 minute or less, 50 seconds or less, 40 seconds or less, or 30 seconds or less, such as 5 seconds to 40 seconds.

Article and system

In a second aspect, an article is provided. An article comprising a plurality of layers of at least one photopolymerizable crosslinking composition, the article comprising 0.1% or less by weight of an extractable component based on the total weight of the article when extracted with a 5% by volume aqueous ethanol solution, the article prepared by a process comprising:

a) Obtaining a photopolymerizable composition;

b) Selectively curing the photopolymerizable composition using actinic radiation to form an article comprising a plurality of layers of at least one photopolymerizable composition;

c) Removing excess photopolymerizable composition from the article;

d) Placing the article in an apparatus according to the first aspect;

e) Inputting a post-cure program or accessing a saved post-cure program through a user interface, the post-cure program comprising: 1) The light intensity provided by at least two LEDs; 2) The length of time of the light provided by the at least two LEDs; and at least one of the following: 3a) A delay time between initiation of light provided by the at least two LEDs and initiation of pumping by the vacuum pump, or 3 b) a delay time between initiation of pumping vacuum on the interior of the chamber by the vacuum pump and initiation of light provided by the at least two LEDs; and

F) The post cure procedure was run.

Referring to fig. 4, the article may be prepared by a process comprising: obtaining a photopolymerizable composition 410; selectively curing the photopolymerizable composition using actinic radiation to form an article 420 comprising a plurality of layers of at least one photopolymerizable composition; and removing excess photopolymerizable composition 430 from the article. Next, the article is placed 440 in a device (e.g., as described in detail above with respect to the first aspect), after which a post-cure program is entered or saved post-cure program 450 is accessed through a user interface and post-cure program 460 is run. The post-cure procedure included: 1) Light intensity provided by at least two light sources (e.g., LEDs); 2) The length of time of the light provided by the at least two light sources; and at least one of the following: 3a) A delay time between initiation of light provided by the light source and initiation of evacuation by the vacuum pump, or 3 b) a delay time between initiation of evacuation by the vacuum pump on the interior of the chamber and initiation of light provided by the light source. Suitable light intensities and times are as described above in relation to the device.

In one embodiment, the post-curing procedure includes turning on the first light source for a predetermined amount of time, followed by turning on the second light source for a predetermined amount of time, wherein the amounts of time may be the same or different. The first light source and the second light source may be employed during a portion of the overlap time or during a non-overlap time. Optionally, the first light source may provide a different wavelength (or range of wavelengths) and/or intensity than the second light source.

In some embodiments, the post-cure program is entered through a user interface shortly before it is run. In some embodiments, the post-cure program is stored in the memory of the processor as it is pre-installed by the device manufacturer or entered and saved by the user. To save a program, after each operating parameter has been selected for the program, the user may activate (e.g., press and hold a program switch, such as any of the P1, P2, or P3 buttons 144 shown in fig. 1E) for up to several seconds to save the entered program to the program switch. When the saved program is subsequently being accessed, the user may simply select the program by activating the program switch to which the program is saved (e.g., pressing a button, turning a knob, touching the touch sensor display somewhere, etc.).

In some embodiments, after the post-curing procedure, when extracted with a 5 volume% aqueous ethanol solution, the article comprises 0.1 wt% or less of the extractable component, 0.9 wt% or less, 0.8 wt% or less, 0.7 wt% or less, 0.6 wt% or less, 0.5 wt% or less, or 0.4 wt% or less of the extractable component, based on the total weight of the article; and when extracted with a 5% by volume aqueous ethanol solution, 0.01% by weight or more, 0.03% by weight or more, 0.05% by weight or more, 0.07% by weight or more, or 0.1% by weight or more of an extractable component based on the total weight of the product. Suitable test procedures for determining the amount of extractable components include: the preparation with a total surface area of 45cm ² was placed in a 40 milliliter (mL) glass vial and the vial was weighed. 15mL of solvent (5 vol% ethanol/Milli-Q water) was added to the vial and there was one 15mL blank (vial with solvent but no preparation). The vial was capped with a TEFLON bottle and the sample was left at 37 ℃ for 24 hours while shaking in a shaker (e.g., a 4638 model LabLine bench incubation shaker) at 80 Revolutions Per Minute (RPM). The sample was allowed to cool before transferring the extraction solution to a new 20mL glass vial. A 5mL aliquot was transferred to a pre-weighed 8mL glass vial and set to gasify under a nitrogen purge. Once the solvent had evaporated, the vials were again weighed until a constant weight was reached. Residual% was calculated using the following formula. The tests are typically completed in triplicate, all performed simultaneously, and the results are the average of the replicates.

Various photopolymerizable compositions are suitable for use in the methods according to the present disclosure. These compositions include at least one polymerizable component. The term "component" encompasses compounds, monomers, oligomers, and polymers. For purposes of reference herein, a "polymerizable component" comprises a hardenable component that can be cured to provide a printed article. For example, in some embodiments, hardening includes irradiation with actinic radiation of sufficient energy to initiate a polymerization or crosslinking reaction. For example, in some embodiments, ultraviolet (UV) radiation, electron beam radiation, or both may be used.

In any embodiment, the photopolymerizable composition comprises at least one of the following: a (meth) acryl component, an epoxy component, a polyalkylene oxide component, a polyester component, a polycarbonate component, a urethane component, a polyamide component, a thiol component, and an alkene component other than a (meth) acryl component, or a combination thereof. In some embodiments, the photopolymerizable composition comprises a combination of a (meth) acryl component and one or more of the following: an epoxy component, a polyalkylene oxide component, a polyester component, a polycarbonate component, a urethane component and/or a polyamide component.

Suitable photopolymerizable compositions include, for example, but are not limited to, those described in detail in the following commonly owned applications: international application PCT/IB2019/059351 (case number 81316) (Klun et al); international applications PCT/IB2019/055413 (Wu et al), PCT/IB2019/055455 (Klun et al), PCT/US2019/033252 (Klun et al) and PCT/IB2019/051815 (Abuelyaman et al); and published applications WO2019/103855 (Parkar et al), WO 2019/02399 (Parkar et al), WO2019/104072 (Chakraborty et al), WO 2019/104079 (Chakraborty et al), WO 2018/119026 (Parkar et al), US 2008/024842 (Cinader et al), WO 2016/191538, WO 2016/191162 (Mayr et al), WO2018/231583 (hermmann et al), and WO 2018/038954 (Raia et al). These patent applications are incorporated by reference herein in their entirety. Suitable articles that can be prepared using the photopolymerizable composition include, for example, but are not limited to, dental articles, such as those used for crowns, bridges, veneers, inlays, onlays, fillings, and dentures (e.g., partial or complete dentures); and orthodontic appliances and devices such as orthodontic brackets, buccal tubes, lingual retainers, orthodontic bands, class II and class III aligners, sleep apnea devices, bite openers, buttons, splints and other attachment devices. In selected embodiments, the article is an orthodontic article or a dental restoration.

In certain embodiments, the photopolymerizable composition comprises a (meth) acryl polymer and at least one ceramic material, a urethane (meth) acryl polymer, a polyalkylene oxide urethane (meth) acryl polymer, a polyester urethane (meth) acryl polymer, a polycarbonate urethane (meth) acryl polymer, a polyamide polymer, an epoxy (meth) acrylate polymer, a thioether polymer, or any combination thereof. In one embodiment, the photopolymerizable composition comprises a (meth) acryl polymer and at least one ceramic material. In one embodiment, the photopolymerizable composition comprises a polycarbonate urethane (meth) acryl polymer. The term "(meth) acrylate" as used herein is a shorthand for acrylate, methacrylate, or combinations thereof; "(meth) acrylic" is a shorthand for acrylic, methacrylic, or a combination thereof; "(meth) acryl" is a shorthand form of acryl and methacryl. "acryl" refers to derivatives of acrylic acid such as acrylate, methacrylate, acrylamide, and methacrylamide. "(meth) acryl" refers to a monomer or oligomer having at least one acryl or methacryl group and, if two or more groups are included, linked by an aliphatic segment. As used herein, "(meth) acrylate functional compounds" are compounds that include, among other things, a (meth) acrylate moiety.

In some embodiments, the photopolymerizable composition comprises ceramic particles as the ceramic material. As used herein, "ceramic particles" include particles of amorphous materials, glass, crystalline ceramics, glass ceramics, and combinations thereof, and refer to non-metallic materials produced by the application of heat or made by chemical synthesis processes. Ceramic particles are generally classified as inorganic materials. The term "amorphous material" in relation to ceramic particles refers to materials derived from the melt and/or gas phase as well as materials made by chemical synthesis, wherein the materials lack a long range crystal structure as determined by x-ray diffraction and/or have an exothermic peak corresponding to crystallization of the amorphous material as determined by Differential Thermal Analysis (DTA). For example, amorphous silica nanoparticles can be produced by the condensation of silanes to form nanoparticles.

In many embodiments, the optional ceramic particles comprise metal oxide ceramic particles, non-oxide ceramic particles, or any combination thereof.

Preferably, the ceramic particles are selected from: zirconia (ZrO ₂), silica (SiO ₂), alumina (Al ₂O₃), yttria (Y ₂O₃), ceria (CeO ₂), magnesium-magnesia-aluminate (MMA) magnesium oxide (MgO), hydroxyapatite (Ca ₅(PO₄)₃ OH), fluoroapatite (Ca ₅(PO₄)₃ F), chloroapatite (Ca ₅(PO₄)₃ Cl), calcite (CaCO ₃), and, Cordierite (Mg ₂Al₄Si₅O₁₈), silicon carbide (SiC), silicon nitride (Si ₃N₄), boron carbide (B ₄ C), titanium diboride (TiB ₂), zirconium diboride (ZrB ₂), boron Nitride (BN), titanium carbide (TiC), zirconium carbide (ZrC), aluminum nitride (AlN), calcium hexaboride (CaB ₆), MAX phase ternary lamellar carbon (nitrogen) compound (M _n+1AX_n), and any combinations thereof. In selected embodiments, high purity particles are used, wherein the total content of metal impurities is preferably less than 100ppm, particularly preferably less than 50ppm. In an alternative embodiment, particles having a total content of metal impurities of about 2,000ppm are used. Suitable ceramic particles are described in detail in commonly owned application __ (docket number 81937).

In some embodiments, the photopolymerizable composition, which may be a slurry or sol, comprises 20 wt% or more, 21 wt% or more, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 32 wt%, or 35 wt% or more of ceramic particles based on the total weight of the photopolymerizable composition; and 60 wt% or less, 29.5 wt% or less, 28.5 wt% or less, 27.5 wt% or less, 26.5 wt% or less, 25.5 wt% or less, or 24.5 wt% or less of ceramic particles based on the total weight of the photopolymerizable composition. In some embodiments, the photopolymerizable composition (e.g., slurry or sol) comprises 3 volume percent (vol%) or greater, 4 vol%, 5 vol%, 6 vol%, 7 vol%, 8 vol%, 9 vol%, 10 vol%, 11 vol%, 12 vol%, 13 vol%, 14 vol%, 15 vol%, 17 vol%, 19 vol%, 21 vol%, 23 vol%, 25 vol%, or 29 vol% or greater ceramic particles based on the total volume of the photopolymerizable composition; and 45% by volume or less, 44% by volume, 42% by volume, 40% by volume, 38% by volume, 36% by volume, 34% by volume, 32% by volume, or 30% by volume or less of ceramic particles based on the total volume of the photopolymerizable composition.

As used herein, "sol" refers to a continuous liquid phase comprising discrete particles ranging in size from 1 nanometer (nm) to 100 nm. "slurry" refers to a continuous liquid phase comprising discrete particles having a size in the range of greater than 100nm to 50 microns or greater than 100nm to 10 microns. The slurry may also optionally comprise discrete particles having a size in the range of 1 nanometer (nm) to 100 nm. As used herein, "particle" refers to a substance that is a solid having a geometrically determinable shape. The shape may be regular or irregular. The particles can generally be analyzed in terms of, for example, particle size and particle size distribution. The particles may comprise one or more crystallites. Thus, the particles may comprise one or more crystalline phases.

Ceramic particles typically have an average particle size diameter (i.e., D ₅₀) of 1 nanometer (nm) or greater 、3nm、4nm、5nm、6nm、7nm、8nm、9nm、10nm、12nm、15nm、17nm、20nm、25nm、30nm、40nm、50nm、60nm、75nm、90nm、100nm、125nm、150nm、175nm、200nm、225nm、250nm、350nm、500nm、750nm、1 microns, 1.25 microns, 1.5 microns, 1.75 microns, 2 microns, 2.5 microns, 3.0 microns, 3.5 microns, 4.0 microns, or 4.5 microns or greater; and D ₅₀ of 10 microns or less, 9.5 microns, 9 microns, 8.5 microns, 8 microns, 7.5 microns, 7 microns, 6.5 microns, 6 microns, 5.5 microns, 5 microns, 4.5 microns, 3 microns, 2 microns, 1.5 microns, 1 micron, 900nm, 800nm, 700nm, 600nm, 500nm, 400nm, 300nm, or 250nm or less. The average particle size (D ₅₀) refers to the particle diameter at which 50% by volume of the particles in the particle distribution have a diameter of this diameter or less, as measured by scanning electron microscopy or transmission electron microscopy. Preferably, the average particle size is the size of the primary particles.

The photopolymerizable compositions of the present disclosure generally comprise at least one photoinitiator. Suitable exemplary photoinitiators are those available under the trade name OMNIRAD from IGM resins company (IGM RESINS (Waalwijk, THE NETHERLANDS)) of wal Wei Ke, the netherlands, and include 1-hydroxycyclohexyl phenyl ketone (OMNIRAD 184), 2-dimethoxy-1, 2-diphenylethan-1-ONE (OMNIRAD 651), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (OMNIRAD 819), 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-ONE (OMNIRAD 2959), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (OMNIRAD 369), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-ONE (OMNIRAD 379), 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-ONE (OMNIRAD), oligo [ 2-hydroxy-1-methyl ] phenyl ] butanone (OMNIRAD) and (37, propiophenone, the company of ralston, the company of rales, the company, the netherlands, the company (37, the company) 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 1173), 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide (OMNIRAD TPO), and 2,4, 6-trimethylbenzoyl phenyl phosphinate (OMNIRAD TPO-L). Additional suitable photoinitiators include, for example and without limitation, benzyl dimethyl ketal, 2-methyl-2-hydroxy propiophenone, benzoin methyl ether, benzoin isopropyl ether, anisoin methyl ether, aromatic sulfonyl chloride, photoactive oximes, and combinations thereof. In some embodiments, the cationic photoinitiator is present in, for example, a composition comprising an epoxy component. Furthermore, thermal initiators may optionally be present in the photopolymerizable compositions described herein. For example, a free radical photoinitiator, a cationic photoinitiator, a thermal photoinitiator, or any combination thereof may be present in the photopolymerizable composition.

Suitable cationic photoinitiators include, for example, but are not limited to, bis [ 4-diphenylsulfonylphenyl ] sulfide bis hexafluoroantimonate, thiophenoxyphenyl sulfonium hexafluoroantimonate (commercially available as CHIVACURE1176 from Qititanium Inc. (Chitec, houston, TX), tris (4- (4-acetylphenyl) phenylthio) sulfonium tetrakis (pentafluorophenyl) borate, tris (4- (4-acetylphenyl) phenylthio) sulfonium tris [ (trifluoromethyl) sulfonyl ] methide and tris (4- (4-acetylphenyl) phenylthio) sulfonium hexafluorophosphate, [4- (1-methylethyl) phenyl ] (4-methylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4- [4- (2-chlorobenzoyl) -phenylthio ] phenyl bis (4-fluorophenyl) sulfonium hexafluoroantimonate, and aromatic sulfonium salts having (PF _6-m(C_nF_2n+1)_m)^- anions, where m is an integer from 1 to 5, n is an integer from 1 to 4 (commercially available as CPI-200K or CPI-200S, which is a monovalent sulfonium salt available from San-Apro Ltd., kyoto, JP) of Kyoto San-Apro Co., ltd., TK-1 available from San-Apro Co., or HS-1 available from San-Apro Co., ltd.).

In some embodiments, the photoinitiator is present in the photopolymerizable composition in an amount of up to about 5% by weight based on the total weight of polymerizable components in the photopolymerizable composition (e.g., excluding components such as ceramic particles). In some cases, the photoinitiator is present in an amount of about 0.1 to 5 wt%, 0.2 to 5 wt%, or 0.5 to 5 wt%, based on the total weight of the photopolymerizable composition.

In some embodiments, the thermal initiator is present in the photopolymerizable composition in an amount of up to about 5 weight percent based on the total weight of polymerizable components in the photopolymerizable composition. In some cases, the thermal initiator is present in an amount of about 0.1 wt% to 5 wt%, based on the total weight of polymerizable components in the photopolymerizable composition. Examples of suitable thermal initiators include, for example, but are not limited to, peroxides such as benzoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide, hydroperoxides (e.g., t-butyl hydroperoxide and cumene hydroperoxide), dicyclohexyl peroxydicarbonate, 2-azo-bis (isobutyronitrile), and t-butyl perbenzoate. Examples of commercially available thermal initiators include initiators available from DuPont specialty chemicals company (DuPont SPECIALTY CHEMICAL (Wilmington, DE)) under the trade name VAZO, including VAZO 67 (2, 2' -azo-bis (2-methylbutyronitrile)), VAZO 64 (2, 2' -azo-bis (isobutyronitrile)) and VAZO 52 (2, 2' -azo-bis (2, 2-dimethylpentanenitril)), and initiators available from north american elvus alto company (Elf Atochem North America (philiadelphia, PA)) under the trade name LUCIDOL, philadelphia, PA.

In some embodiments of the composition comprising a free radical polymerizable component, the composition comprises: a first free radical photoinitiator having sufficient absorbance at a first wavelength range; and a second free radical initiator selected from a second photoinitiator or a thermal free radical initiator having sufficient absorbance at a second wavelength range, wherein the second wavelength range is different from the first wavelength range. Some suitable first radical photoinitiators include, for example, but are not limited to, acyl phosphine oxides and alkyl amine acetophenones. Some suitable second radical photoinitiators include, for example, but are not limited to, photoinitiators comprising a photoinitiator group selected from the group consisting of biphenyl acyl ketals or hydroxyacetophenones. Suitable thermal radical initiators may comprise peroxide or azo groups. Additional details regarding such combinations of a first free radical photoinitiator with a thermal free radical initiator or a second free radical photoinitiator are described in commonly owned international patent application PCT/US2018/062085 (Chakrborty et al).

In some embodiments of compositions comprising a free radical polymerizable component, the composition comprises a polymer or macromolecule having a free radical photoinitiator group, e.g., comprising a polymer or macromolecule backbone and a photoinitiator side group. Suitable photoinitiator groups include, for example, but are not limited to, hydroxy or alkylaminoacetophenone photoinitiators. Additional details regarding such polymers and macromolecules comprising free radical photoinitiator groups are described in commonly owned international patent application PCT/US2018/062074 (Chakrborty et al).

In certain aspects, the use of more than one initiator helps to increase the percentage of monomer incorporated into the reaction product of the polymerizable component and thus reduce the percentage of monomer that remains uncured.

Data representing the article may be generated using computer modeling such as Computer Aided Design (CAD) data. Image data representing the (e.g., polymer) article design may be exported into the layup manufacturing facility in STL format or in any other suitable computer-processable format. Scanning methods may also be employed to scan three-dimensional objects to generate data representative of the article. One exemplary technique for acquiring data is digital scanning. The article may be scanned using any other suitable scanning technique, including radiography, laser scanning, computed Tomography (CT), magnetic Resonance Imaging (MRI), and ultrasound imaging. Other possible scanning methods are described in U.S. patent application publication 2007/0031791 (Cinader, jr. Et al). An initial digital data set, which may include both the raw data from the scanning operation and data representative of the article derived from the raw data, may be processed to segment the article design from any surrounding structure (e.g., the support of the article). In selected embodiments, the scanning technique may include, for example, scanning the patient's mouth to customize the patient's orthodontic article.

Typically, a machine readable medium is provided as part of a computing device. The computing device may have one or more processors, volatile memory (RAM), means for reading a machine-readable medium, and input/output devices such as a display, keyboard, and pointing device. In addition, the computing device may also include other software, firmware, or a combination thereof, such as an operating system and other application software. The computing device may be, for example, a workstation, a laptop computer, a Personal Digital Assistant (PDA), a server, a mainframe, or any other general purpose or application specific computing device. The computing device may read executable software instructions from a computer readable medium, such as a hard disk, CD-ROM, or computer memory, or may receive instructions from another source, such as another networked computer, logically connected to the computer. With reference to fig. 10, a computing device 1000 typically includes an internal processor 1080, a display 1100 (e.g., a monitor), and one or more input devices such as a keyboard 1140 and a mouse 1120. In fig. 10, a dental crown 1130 is shown on a display 1100.

Referring to fig. 6, a system 600 is provided that can be used to form an article. The system 600 includes a display 620 that displays a 3D model 610 of an article (e.g., a dental crown 1130 as shown on display 1100 of fig. 10); and one or more processors 630, responsive to the 3D model 610 selected by the user, to cause the 3D printer/layup manufacturing apparatus 650 to generate a physical object of the article 660. Typically, an input device 640 (e.g., a keyboard and/or mouse) is used with the display 620 and the at least one processor 630, particularly for a user to select the 3D model 610.

Referring to fig. 7, a processor 720 (or more than one processor) communicates with each of a machine-readable medium 710 (e.g., a non-transitory medium), a 3D printer/overlay manufacturing device 740, and optionally a display 730 for viewing by a user. The 3D printer/overlay manufacturing apparatus 740 is configured to prepare one or more articles 750 based on instructions from the processor 720 that provide data from the machine-readable medium 710 representing a 3D model of the article 750 (e.g., the aligner article 1130 shown on the display 1100 of fig. 10).

Referring to fig. 8, for example and without limitation, a layup manufacturing method includes retrieving 810 data representing a 3D model of an article of manufacture in accordance with at least one embodiment of the present disclosure from a (e.g., non-transitory) machine readable medium. The method also includes executing 820, by the one or more processors, a layup manufacturing application interfacing with the manufacturing device using the data; and generating 830, by the manufacturing apparatus, the physical object of the article. For example, the laminate manufacturing apparatus may selectively cure the photopolymerizable composition to form an article having multiple layers. One or more of various optional post-processing steps 840 may be performed. Typically, the remaining unpolymerized photopolymerizable component may be cured, such as in an apparatus according to the first aspect.

Additionally, referring to fig. 9, a method of preparing an article includes receiving 910, by a manufacturing apparatus having one or more processors, a digital object containing data specifying a plurality of layers of the article; and generating 920 the article by a layup manufacturing process using the manufacturing apparatus based on the digital object. Likewise, the article may undergo one or more steps of post-treatment 930.

FIG. 2 illustrates an exemplary stereolithography apparatus ("SLA") that can be used with the photopolymerizable compositions and methods described herein. In general, SLA 200 may include a laser 202, optics 204, steering lens 206, elevator 208, platform 210, and straight edge 212 within a cylinder 214 filled with a photopolymerizable composition. In operation, the laser 202 is directed across the surface of the photopolymerizable composition to cure a cross-section of the photopolymerizable composition, after which the lift 208 slightly lowers the platform 210 and another cross-section is cured. The straight edges 212 may scan the surface of the cured composition between layers to smooth and normalize the surface before adding a new layer. In other embodiments, the cylinder 214 may be slowly filled with liquid resin as the article is stretched layer-by-layer onto the top surface of the photopolymerizable composition.

The related art, namely, the compatibilization polymerization involving digital light processing ("DLP"), also employs containers of curable polymers (e.g., photopolymerizable compositions). However, in DLP-based systems, a two-dimensional cross-section is projected onto a curable material to cure a desired portion transverse to the entire plane of the projected beam at one time. All such curable polymer systems that may be suitable for use with the photopolymerizable compositions described herein are intended to fall within the scope of the term "compatibilized polymerization system" as used herein. In certain embodiments, devices suitable for use in continuous mode may be employed, such as those commercially available from Carbon 3D company (Carbon 3D, inc. (Redwood City, CA)) of Redwood, california, as described, for example, in U.S. patent 9,205,601 and 9,360,757 (both to DeSimone et al).

More generally, the photopolymerizable composition is generally cured using actinic radiation such as ultraviolet radiation, electron beam radiation, visible light radiation, or any combination thereof. One skilled in the art can select the appropriate radiation source and wavelength range for a particular application without undue experimentation.

After the 3D article is formed, it is typically removed from the laminate manufacturing apparatus and rinsed (e.g., ultrasonic or bubbling or spray rinsing in a solvent), which will dissolve a portion of the uncured photopolymerizable composition, but not the cured solid article (e.g., the green body). Any other conventional method for cleaning the article and removing uncured material from the surface of the article may also be utilized. In some embodiments, removing the uncured material at the surface of the article includes moving the article and thereby generating a mass inertia force in the uncured photopolymerizable composition disposed on the article, thereby forming a coating of the uncured photopolymerizable composition on the article. The mass inertial force may be generated using a centrifuge, shaker, or mixer that spins along one or more axes. Suitable ways of generating the mass inertial force are described, for example, in commonly owned International application PCT/IB2020050451 (docket No. 81682) (chakroberty et al), which is incorporated herein by reference in its entirety. For example, a centrifuge, shaker, or mixer that spins along one or more axes may be used to generate a source of mass inertial force. In some embodiments, the movement of the object is a rotation or spin of the object. Thus, the mass inertia force may be generated by centrifugal force. One suitable mixer that spins along more than one axis is a biaxial asymmetric centrifugal mixer, such as DAC 400FVZ available from fluckek, landrum, SC, of landmer, south carolina. The biaxial asymmetric centrifugal mixer provides simultaneous biaxial spin which automatically reorients the article during spin, which tends to pull uncured composition away from the concave features of the article in a short period of time (e.g., 20 seconds or less, 15 seconds or less, or 10 seconds or less).

In a fifth aspect, a system is provided. The system comprises:

a) An apparatus according to an embodiment of the first aspect; and

B) An article comprising at least one photopolymerizable composition.

In some embodiments, the article may be as described in detail above with respect to the second aspect. Optionally, the article comprises multiple layers of at least one photopolymerizable composition. Fig. 1B-1D illustrate suitable systems, each including an apparatus 1000 and an article 180 (e.g., a dental crown). When placed in the chamber of the apparatus, the article is typically partially cured.

Method of

In a third aspect, a method of post-curing an article is provided. The method comprises the following steps:

a) Obtaining an article;

b) Placing the article in an apparatus comprising:

1) A housing;

2) A chamber disposed in the housing;

3) At least one light source disposed within the housing;

4) A user interface disposed on an exterior of the housing, the user interface including a display and a plurality of program switches configured to adjust at least three operating parameters of the device; and

5) A vacuum pump operatively connected to the chamber;

c) Inputting a post-cure program or accessing a saved post-cure program through a user interface, the post-cure program comprising: 1) Light intensity provided by at least one light source; 2) The length of time of the light provided by the at least one light source; and at least one of the following: 3a) A delay time between initiation of light provided by the at least one light source and initiation of pumping by the vacuum pump, or 3 b) a delay time between initiation of pumping vacuum on the interior of the chamber by the vacuum pump and initiation of light provided by the at least one light source; and

D) The post cure procedure was run.

In a fourth aspect, another article is provided. The article is prepared by a method according to an embodiment of the third aspect. In some embodiments, the article comprises an orthodontic article or a dental restoration.

Referring to fig. 5, the post-cured article may include: obtaining 510 and placing 520 the article in an apparatus (e.g., an apparatus according to the first aspect). The method further comprises the steps of: the post-cure program is entered or saved 530 and run 540 by the user interface. The program includes: 1) Light intensity provided by at least one light source; 2) The length of time of the light provided by the at least one light source; and at least one of the following: 3a) A delay time between initiation of light provided by the at least one light source and initiation of pumping by the vacuum pump, or 3 b) a delay time between initiation of pumping vacuum on the interior of the chamber by the vacuum pump and initiation of light provided by the at least one light source. Suitable light sources include, for example, but are not limited to, LEDs, UV lamps, fluorescent tubes, and lasers. In certain embodiments, two light sources, three light sources, four light sources, or more light sources are used. As mentioned above, a single light source located in one location also encompasses an array located in that location.

In some embodiments, the article may be formed using laminate manufacturing, such as described in detail above. The article optionally includes multiple layers of at least one photopolymerizable composition, which may be provided by: obtaining a photopolymerizable composition; selectively curing the photopolymerizable composition using actinic radiation to form an article comprising a plurality of layers of at least one photopolymerizable composition; and removing excess photopolymerizable composition from the article. Suitable photopolymerizable compositions and photopolymerizable compositions are discussed in detail above with respect to the articles.

In some embodiments, the article may be formed using a method such as casting or molding.

Selected embodiments of the present disclosure

Embodiment 1 is an apparatus. The apparatus includes: a) A housing; b) A chamber disposed in the housing; c) At least two Light Emitting Diodes (LEDs) disposed within the housing; and a user interface disposed on an exterior of the housing. The chamber is configured to be adaptable to each of an open configuration, a closed configuration, and a hermetically sealed configuration, and the chamber comprises a material transparent to actinic radiation. Light from the at least two LEDs enters the chamber from more than one direction. The user interface includes a display and a plurality of program switches configured to adjust at least three operating parameters of the device. The apparatus also includes a vacuum pump operatively connected to the chamber.

Embodiment 2 is the apparatus of embodiment 1, wherein the at least three operating parameters include: 1) The light intensity provided by the at least two LEDs; 2) The length of time of the light provided by the at least two LEDs; and 3) a delay time between initiation of light provided by the at least two LEDs and initiation of evacuation of the vacuum on the interior of the chamber by the vacuum pump.

Embodiment 3 is the apparatus of embodiment 1, wherein the at least three operating parameters include: 1) The light intensity provided by the at least two LEDs; 2) The length of time of the light provided by the at least two LEDs; and 3) a delay time between initiation of the vacuum pump drawing a vacuum on the interior of the chamber and initiation of the light provided by the at least two LEDs.

Embodiment 4 is the apparatus of any one of embodiments 1 to 3, further comprising a processor, wherein the processor causes the at least two LEDs to emit light and causes the vacuum pump to operate according to a program input through the user interface.

Embodiment 5 is the apparatus of embodiment 4, wherein the processor further comprises a memory, and is configured to cause the at least two LEDs to emit light and to cause the vacuum pump to operate according to a program stored in the memory.

Embodiment 6 is the apparatus of any one of embodiments 1 to 5, wherein the chamber comprises a material transparent to actinic radiation having a wavelength of at least between 250 nanometers (nm) and 900 nm.

Embodiment 7 is the method of any one of embodiments 1 to 6, wherein each of the at least two LEDs provides light having a peak wavelength between 250nm and 500 nm.

Embodiment 8 is the device of any one of embodiments 1-7, wherein the first LED is positioned to direct light through a first major surface of the chamber and the second LED is positioned to direct light through an opposite second major surface of the chamber.

Embodiment 9 is the apparatus of any one of embodiments 1 to 8, further comprising a reflective material positioned in the housing to reflect actinic radiation through either the first major surface of the chamber or the opposite second major surface of the chamber.

Embodiment 10 is the apparatus of any one of embodiments 1 to 9, wherein the chamber comprises at least two glass walls through which actinic radiation enters the chamber.

Embodiment 11 is the apparatus of any one of embodiments 1 to 10, wherein the chamber comprises at least two quartz walls through which the actinic radiation enters the chamber.

Embodiment 12 is the device of any one of embodiments 1-11, wherein the plurality of program switches comprises at least one button, at least one knob, or a combination thereof.

Embodiment 13 is the device of any one of embodiments 1-12, wherein the user interface includes a touch screen that provides the display and the plurality of program switches.

Embodiment 14 is the method of any one of embodiments 1 to 13, wherein the at least two LEDs provide light having a peak wavelength between 360nm and 460 nm.

Embodiment 15 is the device of any one of embodiments 1-14, further comprising a third LED positioned to direct light through a third major surface of the chamber, wherein the third major surface is directly adjacent to each of the first major surface and the second major surface.

Embodiment 16 is the device of embodiment 15, further comprising a fourth LED positioned to direct light through a fourth major surface of the chamber, wherein the fourth major surface is opposite the third major surface.

Embodiment 17 is the apparatus of any one of embodiments 1 to 16, wherein the first major surface of the chamber is a floor of the chamber and the second major surface of the chamber is a lid of the chamber.

Embodiment 18 is the apparatus of any one of embodiments 1-17, wherein the chamber further comprises a connector configured to attach a gas source to the chamber.

Embodiment 19 is the apparatus of any one of embodiments 1-18, further comprising a three-way valve operably connected to the chamber, the three-way valve configured to operably connect the chamber to the vacuum pump or to the gas source.

Embodiment 20 is the apparatus of any one of embodiments 1-18, further comprising a first valve and a second valve each operatively connected to the chamber, the first valve configured to operatively connect the chamber to the vacuum pump and the second valve operatively connect the chamber to the gas source.

Embodiment 21 is the apparatus of any one of embodiments 18-20, wherein the plurality of program switches are further configured to adjust a time to purge the chamber with gas from the gas source, a pressure to purge the chamber with the gas, or both.

Embodiment 22 is the apparatus of any one of embodiments 18 to 21, wherein the gas source provides an inert gas.

Embodiment 23 is the device of any one of embodiments 1-22, wherein the user interface further comprises an actuation button.

Embodiment 24 is the device of embodiment 23, wherein the actuation button is configured to initiate light provided by the at least two LEDs.

Embodiment 25 is the device of embodiment 24, wherein the start button is configured to initiate a program that has been entered through the user interface.

Embodiment 26 is the apparatus of any one of embodiments 1 to 25, wherein the vacuum pump is disposed outside the enclosure.

Embodiment 27 is the apparatus of any one of embodiments 1 to 26, wherein the vacuum pump is disposed inside the housing.

Embodiment 28 is the apparatus of any one of embodiments 1-27, wherein the vacuum pump is configured to achieve an absolute pressure of 0.1 millibar (mbar) to 30 mbar, 5mbar to 20mbar, or 0.1mbar to 10mbar inside the chamber.

Embodiment 29 is the device of any one of embodiments 1-28, wherein the at least two LEDs provide a light intensity of 50 milliwatts per square centimeter (mW/cm ²) to 500 milliwatts per square centimeter, or 300mW/cm ² to 500mW/cm ².

Embodiment 30 is the device of any one of embodiments 1-29, further comprising at least two LEDs that provide light having a peak wavelength below 360nm, above 460nm, or both.

Embodiment 31 is an article. The article includes multiple layers of at least one photopolymerizable crosslinking composition. In addition, when extraction is performed with a 5% by volume aqueous ethanol solution, the article comprises 0.1% by weight or less of extractable components, based on the total weight of the article. The product is prepared by the following process: a) Obtaining a photopolymerizable composition; b) Selectively curing the photopolymerizable composition using actinic radiation to form an article having a plurality of layers of at least one photopolymerizable composition; c) Removing excess photopolymerizable composition from the article; d) Placing the article in the apparatus of the first aspect; e) Inputting a post-cure program or accessing a saved program through a user interface; and f) running the post-cure program. The post-cure procedure includes: i) The light intensity provided by at least two LEDs; ii) the length of time of the light provided by the at least two LEDs; and at least one of the following: iiia) a delay time between initiation of light provided by the at least two LEDs and initiation of evacuation by a vacuum pump, or iiib) a delay time between initiation of evacuation by the vacuum pump on the interior of the chamber and initiation of light provided by the at least two LEDs.

Embodiment 32 is the article of embodiment 31, wherein the article is an orthodontic article or a dental restoration.

Embodiment 33 is the article of embodiment 31 or embodiment 32, wherein the photopolymerizable composition comprises 20 wt% to 60 wt% ceramic particles based on the total weight of the photopolymerizable composition.

Embodiment 34 is the article of embodiment 31 or embodiment 32, wherein the photopolymerizable composition comprises 3 to 45% by volume of ceramic particles based on the total volume of the photopolymerizable composition.

Embodiment 35 is the article of embodiment 33 or embodiment 34, wherein the ceramic particles comprise metal oxide ceramic particles, non-oxide ceramic particles, or a combination thereof.

Embodiment 36 is the article of any one of embodiments 33 to 35, wherein the ceramic particles are selected from the group consisting of: zirconia, silica, alumina, yttria, ceria, magnesium-magnesia-aluminate (MMA), magnesia, hydroxyapatite, fluoroapatite, chloroapatite, calcite, cordierite, silicon carbide, silicon nitride, boron carbide, titanium diboride, zirconium diboride, boron nitride, titanium carbide, zirconium carbide, aluminum nitride, calcium hexaboride, MAX phase ternary lamellar carbon (nitrogen) compounds, and combinations thereof.

Embodiment 37 is the article of any one of embodiments 31-36, wherein the photopolymerizable composition further comprises at least one photoinitiator.

Embodiment 38 is the article of any one of embodiments 31 to 37, wherein the photopolymerizable composition comprises at least one of: a (meth) acryl component, an epoxy component, a polyalkylene oxide component, a polyester component, a polycarbonate component, a urethane component, a polyamide component, a thiol component, an alkene component other than the (meth) acryl component, or a combination thereof.

Embodiment 39 is the article of any of embodiments 31-38, wherein the photopolymerizable composition comprises a (meth) acryl polymer and at least one ceramic material, urethane (meth) acryl polymer, polyalkylene oxide urethane (meth) acryl polymer, polyester urethane (meth) acryl polymer, polycarbonate urethane (meth) acryl polymer, polyamide polymer, epoxy (meth) acrylate polymer, thioether polymer, or a combination thereof.

Embodiment 40 is a method of post curing an article. The method comprises the following steps: a) Obtaining an article; b) Placing the article in an apparatus; c) Inputting a post-cure program or accessing a saved program through a user interface; and d) running the post-cure program. The apparatus includes: 1) A housing; 2) A chamber disposed in the housing; 3) At least one light source disposed within the housing; 4) A user interface disposed on an exterior of the housing, the user interface comprising a display and a plurality of program switches configured to adjust at least three operating parameters of the device; and 5) a vacuum pump operatively connected to the chamber. The post-cure procedure includes: i) Light intensity provided by at least one light source; ii) a length of time of light provided by the at least one light source; and at least one of the following: iiia) a delay time between initiation of light provided by the at least one light source and initiation of evacuation by a vacuum pump, or iiib) a delay time between initiation of evacuation by the vacuum pump on the interior of the chamber and initiation of light provided by the at least one light source.

Embodiment 41 is the method of embodiment 40, wherein the chamber is configured to be adaptable to each of an open configuration, a closed configuration, and a hermetically sealed configuration.

Embodiment 42 is the method of embodiment 40 or embodiment 41, wherein the chamber comprises a material transparent to actinic radiation having a wavelength of at least between 250 nanometers (nm) and 900 nm.

Embodiment 43 is the method of any one of embodiments 40-42, wherein the at least one light source comprises a Light Emitting Diode (LED).

Embodiment 44 is the method of embodiment 43, wherein the at least one LED provides light having a peak wavelength between 250nm and 500 nm.

Embodiment 45 is the method of any one of embodiments 40-44, wherein a first LED is positioned to direct light through a first major surface of the chamber and a second LED is positioned to direct light through an opposite second major surface of the chamber.

Embodiment 46 is the method of any of embodiments 40-45, the apparatus further comprising a reflective material positioned in the enclosure to reflect actinic radiation through either the first major surface of the chamber or the opposite second major surface of the chamber.

Embodiment 47 is the method of any one of embodiments 40 to 46, wherein the article is formed using laminate manufacturing.

Embodiment 48 is the method of any one of embodiments 40-47, wherein providing the article comprises: i) Obtaining a photopolymerizable composition; II) selectively curing the photopolymerizable composition using actinic radiation to form an article comprising a plurality of layers of at least one photopolymerizable composition; and III) removing excess photopolymerizable composition from the article.

Embodiment 49 is an article of manufacture made by the method of any one of embodiments 40-48.

Embodiment 50 is the article of embodiment 49, wherein the article is an orthodontic article or a dental restoration.

Embodiment 51 is the article of embodiment 49 or embodiment 50, comprising 0.1 wt% or less of an extractable component, based on the total weight of the article, when extracted with a 5 vol% aqueous ethanol solution.

Embodiment 52 is a system. The system comprises: a) The apparatus according to any one of embodiments 1 to 30; and b) an article comprising at least one photopolymerizable composition.

Embodiment 53 is the system of embodiment 52, wherein the article comprises multiple layers of at least one photopolymerizable composition.

Embodiment 54 is the system of embodiment 52 or 53, wherein the article is partially cured.

Embodiment 55 is the system of any one of embodiments 52-54, wherein the article is an orthodontic article or a dental restoration.

Examples

Although the objects and advantages of this disclosure are further illustrated by the following examples, the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure. Unless otherwise indicated or otherwise readily apparent from the context, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight.

Example 1-hypothetical example

Crowns were constructed using 3M ESPE SINFONY paste (3 MESPE (3M ESPE,St.Paul,Mn) from St. Paul, minnesota) by layering at least one selected color paste (e.g., including Opaque paste O A0-O D4, dentin paste D A0-D D, incisal paste E1-E4, transmission-Opaque paste IO 1-IO 5, opaque-Dentin paste DO1-DO 5, enamel-effect paste E5-E6, MAGIC INTENSIVE paste I1-I11, and/or Transparent-Opal paste T1-T4) on a model, each layer having a maximum thickness of 1 millimeter. Each layer was polymerized using a VISIO Alfa curing apparatus (available from 3M ESPE) before the next layer was applied. Next, the crown is lifted from the model and placed in the device according to the first aspect described in detail above. The final polymerization of the dental crowns was carried out in the apparatus with a light exposure of 1 minute using a wavelength spectrum of 400nm-500nm without vacuum, followed by a light exposure of 14 minutes also at a wavelength spectrum of 400nm-500nm with a vacuum of 0.1 mbar.

All of the above-mentioned patents and patent applications are hereby expressly incorporated by reference. The above embodiments are all examples of the present invention, and other configurations are also possible. Accordingly, the invention should not be considered limited to the embodiments described in detail above and illustrated in the drawings, but is to be defined only by the proper scope of the appended claims and equivalents thereof.

Claims (16)

1. An apparatus, the apparatus comprising:

a) A housing;

b) A chamber disposed in the housing, the chamber configured to be adaptable to each of an open configuration, a closed configuration, and a hermetically sealed configuration, wherein the chamber comprises a material transparent to actinic radiation;

c) At least two Light Emitting Diodes (LEDs) disposed within the housing, wherein light from the at least two LEDs enters the chamber from more than one direction;

d) A user interface disposed on an exterior of the housing, the user interface comprising a display and a plurality of program switches configured to adjust at least three operating parameters of the device, wherein the at least three operating parameters comprise: 1) The light intensity provided by the at least two LEDs; 2) The length of time of the light provided by the at least two LEDs; and at least one of the following: 3a) A delay time between initiation of light provided by the at least two LEDs and initiation of evacuation of the interior of the chamber by a vacuum pump, or 3 b) a delay time between initiation of evacuation of the interior of the chamber by a vacuum pump and initiation of light provided by the at least two LEDs; and

E) A vacuum pump operatively connected to the chamber.

2. The apparatus of claim 1, further comprising a processor, wherein the processor causes the at least two LEDs to emit light and the vacuum pump to operate according to a program entered through the user interface.

3. The apparatus of claim 2, wherein the processor further comprises a memory and is configured to cause the at least two LEDs to emit light and the vacuum pump to operate according to a program stored in the memory.

4. The apparatus of claim 1, wherein a first LED is positioned to direct light through a first major surface of the chamber and a second LED is positioned to direct light through an opposite second major surface of the chamber.

5. The device of claim 1, wherein the user interface comprises a touch screen that provides the display and the plurality of program switches.

6. The apparatus of claim 1, further comprising a third LED positioned to direct light through a third major surface of the chamber, wherein the third major surface is directly adjacent to each of the first and second major surfaces.

7. The apparatus of claim 1, wherein the chamber further comprises a connector configured to attach a gas source to the chamber.

8. The apparatus of claim 7, wherein the plurality of program switches are further configured to adjust a time to purge the chamber with gas from the gas source, a pressure to purge the chamber with the gas, or both.

9. The apparatus of claim 1, wherein the vacuum pump is configured to achieve an absolute pressure of 0.1 millibar (mbar) to 30 mbar inside the chamber.

10. A method of post-curing an article, the method comprising:

a) Obtaining an article;

b) Placing the article in an apparatus comprising:

1) A housing;

2) A chamber disposed in the housing;

3) At least one light source disposed within the housing;

4) A user interface disposed on an exterior of the housing, the user interface comprising a display and a plurality of program switches configured to adjust at least three operating parameters of the device; and

5) A vacuum pump operatively connected to the chamber;

c) Inputting a post-cure program or accessing a saved program through the user interface, the post-cure program comprising: 1) The light intensity provided by the at least one light source; 2) The length of time of the light provided by the at least one light source; and at least one of the following: 3a) A delay time between initiation of light provided by the at least one light source and initiation of evacuation by the vacuum pump, or 3 b) a delay time between initiation of evacuation by the vacuum pump on the interior of the chamber and initiation of light provided by the at least one light source; and

D) And running the post-curing program.

11. The method of claim 10, wherein the at least one light source comprises a Light Emitting Diode (LED) that provides light having a peak wavelength between 250nm and 500 nm.

12. The method of claim 10, wherein providing the article comprises:

I) Obtaining a photopolymerizable composition;

II) selectively curing the photopolymerizable composition using actinic radiation to form an article comprising a plurality of layers of at least one photopolymerizable composition; and

III) removing excess photopolymerizable composition from the article.

13. An article prepared by the method of any one of claims 10 to 12.

14. The article of claim 13, wherein the article is an orthodontic article or a dental restoration.

15. The article of claim 13, comprising 0.1% or less by weight of an extractable component based on the total weight of the article when extracted with a 5% by volume aqueous ethanol solution.

16. A system, the system comprising:

a) The apparatus according to any one of claims 1 to 9; and

B) An article comprising at least one photopolymerizable composition.